Details

Autor(en) / Beteiligte

• Zhang, Jingjing
• Yang, Jin‐Dong
• Zheng, Hanliang
• Xue, Xiao‐Song
• Mayr, Herbert
• Cheng, Jin‐Pei

Titel

Exploration of the Synthetic Potential of Electrophilic Trifluoromethylthiolating and Difluoromethylthiolating Reagents

Ist Teil von

• Angewandte Chemie International Edition, 2018-09, Vol.57 (39), p.12690-12695

Auflage

International ed. in English

Ort / Verlag

Germany: Wiley Subscription Services, Inc

Erscheinungsjahr

2018

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The electrophilicity parameters (E) of some trifluoromethylthiolating and difluoromethylthiolating reagents were determined by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters (N, sN), using the linear free‐energy relationship log k2=sN(N+E). The electrophilic reactivities of these reagents cover a range of 17 orders of magnitude, with Shen and Lu's reagent 1 a being the most reactive and Billard's reagent 1 h being the least reactive electrophile. While the observed electrophilic reactivities (E) of the amido‐derived trifluoromethylthiolating reagents correlate well with the calculated Gibbs energies for heterolytic cleavage of the X−SCF3 bonds (Tt+DA), the cumol‐derived reagents 1 f and 1 g are more reactive than expected from the thermodynamics of the O−S cleavage. The E parameters of the tri/difluoromethylthiolating reagents derived in this work provide an ordering principle for their use in synthesis. The electrophilicities (E) of trifluoromethylthiolating and difluoromethylthiolating reagents were investigated by following the kinetics of their reactions with a series of enamines and carbanions with known nucleophilicity parameters. The electrophilicity parameters determined for these reagents cover a reactivity range of 17 orders of magnitude.